CN108896539A - Measure the optofluidic detector of phosphorus content in seawater - Google Patents
Measure the optofluidic detector of phosphorus content in seawater Download PDFInfo
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- CN108896539A CN108896539A CN201810462356.5A CN201810462356A CN108896539A CN 108896539 A CN108896539 A CN 108896539A CN 201810462356 A CN201810462356 A CN 201810462356A CN 108896539 A CN108896539 A CN 108896539A
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- 239000013535 sea water Substances 0.000 title claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 33
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- 239000013307 optical fiber Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000012788 optical film Substances 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 32
- 238000005259 measurement Methods 0.000 claims description 28
- 238000002835 absorbance Methods 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 7
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 4
- 241001672694 Citrus reticulata Species 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 18
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 238000002798 spectrophotometry method Methods 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 6
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- KQROHCSYOGBQGJ-UHFFFAOYSA-N 5-Hydroxytryptophol Chemical compound C1=C(O)C=C2C(CCO)=CNC2=C1 KQROHCSYOGBQGJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 5
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- -1 phosphate anion Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
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- 235000015097 nutrients Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
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- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/775—Indicator and selective membrane
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/7756—Sensor type
- G01N2021/7766—Capillary fill
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/7769—Measurement method of reaction-produced change in sensor
- G01N2021/7789—Cavity or resonator
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/061—Sources
- G01N2201/06113—Coherent sources; lasers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/08—Optical fibres; light guides
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Abstract
The present invention provides a kind of optofluidic detector for measuring phosphorus content in seawater, can be improved the stability of detection process, and guarantees the accurate fixed and accuracy of result, which is characterized in that including：Three miniflow pumps；Inlet portion, comprising pumping the first entrance runner, second entrance runner, the third entrance channel that are connected with three miniflows respectively；Mixing unit includes：Multiple longitudinal miniflow channels arranged in parallel, multiple lateral miniflow channels for connecting adjacent longitudinal miniflow channel, and the multiple semi-circular shape micro-structures being arranged in longitudinal miniflow channel and lateral miniflow channel；Capillary cuvette, entrance are connected with the stream end that goes out for longitudinal miniflow channel that most downstream is arranged in；Optical fiber portion includes two optical fiber, and the front port of two optical fiber, which is mutually arranged oppositely, to be coated with optical film on the left and right sides of capillary cuvette, front port and make to form optical resonator between two ports；And laser source, it is connected with the rear end of an optical fiber, the rear end of another optical fiber is connected with spectrometer.
Description
Technical field
The present invention relates to a kind of optofluidic detectors of phosphorus content in measurement seawater.
Background technique
Seawater monitoring is a pith in environmental monitoring.Phosphate is right as a kind of typical nutrients in sea water
The growth of planktonic organism plays a crucial role in ocean.Understanding substance circulation and prevention marine harmful algae in environment
The proliferation of class, nutrients in sea water monitoring have great significance.The artificial technology of existing monitoring Seawater Phosphate mainly has
Three kinds：Electrochemical methods, Fluorometric assay of fluorescence-labeled method and spectrophotometry.Electrochemical methods contain phosphoric acid in detection high concentration
The liquid of salt has high accuracy, but is not suitable for being used to measure the lower seawater of phosphate concn.Fluorescent marker method has
Selectivity and high accuracy, but fluorescence intensity is easily affected by the external environment.Spectrophotometric analysis method is simple and effective with its,
High sensitivity and accuracy, high reproducibility are widely used in sensor design and seawater monitoring.China ocean nutrition at present
The deficiencies of salt mainly uses based on spot sampling lab analysis, and there are sizes for instrument and equipment greatly, energy consumption is high, the detection obtained
As a result representative and timeliness is not high, it is difficult to support the regulatory requirements such as marine environment bearing capacity monitoring and warning and overall control.
In recent years, with the development of microflow control technique, these disadvantages are overcome.
Optofluidic technology is a frontier interdisciplinary, is quickly grown in recent years.Optofluidic technology combination optics and micro-
Flow control, liquid with precise control in microscopic dimensions.Micro-fluidic chip has size small, and the advantages that fast is reacted in low-loss, can overcome
The deficiency of traditional spectrophotometry measurement nutrients in sea water.But phosphatic mole coefficient is lower, the size of optofluidic chip
It is smaller, signal less stable when detection.
Summary of the invention
The present invention is to carry out in order to solve the above problems, and it is an object of the present invention to provide a kind of light for measuring phosphorus content in seawater
Flow control detector, improves the stability of detection process, and guarantees the accurate fixed and accuracy of testing result.
The present invention to achieve the goals above, uses following scheme.
The present invention provides a kind of optofluidic detector for measuring phosphorus content in seawater, which is characterized in that including：Three miniflows
Pump, pumps the first indicator, liquid to be detected and the second indicator respectively；Inlet portion includes what is be connected respectively with three miniflow pumps
First entrance runner, second entrance runner, third entrance channel；Mixing unit includes：Multiple longitudinal miniflows arranged in parallel
Channel, multiple lateral miniflow channels for connecting adjacent longitudinal miniflow channel, and setting is in longitudinal miniflow channel and lateral miniflow ditch
Multiple semi-circular shape micro-structures in road, be arranged in longitudinal miniflow channel of most upstream become a mandarin end and first entrance runner, the
Two entrance channels are connected with the outlet of third entrance channel；Capillary cuvette, entrance and the longitudinal direction that most downstream is arranged in are micro-
The stream end that goes out of stream channel is connected；Optical fiber portion, includes two optical fiber, and the front port of two optical fiber is mutually arranged oppositely in capillary colorimetric
The left and right sides of pipe, being coated with optical film on two front ports makes to form optical resonator between two ports；And laser source,
It is connected with the rear end of an optical fiber, for emitting laser, wherein the rear end of another optical fiber is connected with spectrometer, makes spectrum
Instrument recording laser passes through the luminous intensity exported after capillary cuvette, and is compared to obtain absorbance value with laser normal intensity.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：Second entrance runner pumps the miniflow pump of liquid to be detected between first entrance runner and third entrance channel
It is connected with second entrance runner.
Preferably, also have such in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
Feature：There are six longitudinal miniflow channel is total, they are successively set as to first to the 6th longitudinal miniflow channel along direction is flowed to, the
The length of one longitudinal miniflow channel is D1, and the equal length of second to the 6th longitudinal miniflow channel is D2, D1：D2=1：1.5
~3, lateral miniflow channel altogether there are five, length is B1, B1：D1=1：1.5~3, all longitudinal direction miniflow channels and transverse direction are micro-
The width for flowing channel is equal, is W, W：D1=1：15~20.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：D1=3256 μm of length of first longitudinal direction miniflow channel, it is D2=6512 μm of length of remaining longitudinal miniflow channel, horizontal
To B1=1628 μm of length of miniflow channel, W=200 μm of width of all miniflow channels.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：At least three semi-circular shape micro-structures are respectively provided in miniflow channel longitudinally in each and each lateral miniflow channel,
The outer diameter of semi-circular shape micro-structure is E, E：W=3~8：12.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：The internal diameter of semi-circular shape micro-structure is 30 μm, and E=60 μm of outer diameter, each transverse direction miniflow channel is interior to be equipped with 6 semicircles
Annular micro-structure is provided with 3 semi-circular shape micro-structures in first longitudinal direction miniflow channel, in second to the 6th longitudinal miniflow ditch
30 semi-circular shape micro-structures are each provided in road, in miniflow channel longitudinally in each and each lateral miniflow channel, adjacent half
Distance of center circle unequally distributed blades between circular ring shape micro-structure, and the center of circle of adjacent semi-circular shape micro-structure is not in straight line
On.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：With 280 μm or 150 μm of distance of center circle unequally distributed blades between adjacent semi-circular shape micro-structure, and semi-circular shape
The opening line and miniflow channel of micro-structure are axial at 60 ° or 120 ° of angle.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：Longitudinal miniflow channel is primary every 1000 μm of bendings, and curved radian is 180 °, 100 μm of curved part internal diameter, outside
300 μm of diameter, arc length is about 628 μm, and such effect is best.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：Optical film is golden film, and the front port of two optical fiber is separately fixed in the left and right side walls of capillary cuvette, and
The end face of front port is flushed with the inner surface of side wall.
Preferably, there can also be this in the optofluidic detector of phosphorus content in measurement seawater according to the present invention
The feature of sample：First indicator and the second indicator are respectively ammonium molybdate solution and antimony tartrate potassium solution.
Preferably, can also include in the optofluidic detector of phosphorus content in measurement seawater according to the present invention：It is useless
Liquid collection portion is connected with the outlet of capillary cuvette；And spectrometer.
The action and effect of invention
The optofluidic detector of phosphorus content in measurement seawater provided by the present invention passes through miniflow channel combination spectrophotometric
Method realizes the Real_time quantitative detection for the phosphate content in seawater, and optical resonator increases while reducing size of devices
The big accuracy of system.The detection limit of optofluidic detector provided by the present invention can reach 0.1 μm of ol/L, measurement range
0.1~100 μm of ol/L, when detection accuracy reachable ± 10%.The present invention is by spectrophotometric analysis method, optical resonator and miniflow
Control combines, and develops Highgrade integration ocean nutritive salt sensing chip using optofluidic technology, has important researching value.
Detailed description of the invention
Fig. 1 be the present embodiments relate to measurement seawater in phosphorus content optofluidic detector structural schematic diagram；
Fig. 2 be the present embodiments relate to miniflow channel in semi-circular shape micro-structure enlarged drawing；
Fig. 3 be the present embodiments relate to mixing unit in liquid mixing effect picture, wherein (a) is the plane of mixing unit
Scheme, be (b) plan view at the longitudinal sectional drawing and micro-structure of channel, is (c) 3-D image of mixing unit entrance and exit；
Fig. 4 is that laser after chromogenic reaction occurs for the indicator that the spectrometer in the embodiment of the present invention detects and liquid to be detected
The incident spectrogram with outgoing；And
Fig. 5 be the present embodiments relate to phosphate standard liquid concentration and absorbance relational graph.
Specific embodiment
It is lower to be elaborated referring to optofluidic detector of the attached drawing to phosphorus content in measurement seawater according to the present invention.
<Embodiment>
As shown in Figure 1, the optofluidic detector 10 of phosphorus content includes in measurement seawater：Three miniflows pump 21 to 23, entrance
Portion 30, mixing unit 40, capillary cuvette 50, optical fiber portion 60, laser source 70, spectrometer 80 and waste collection portion 90.
Three miniflow pumps 21 to 23 are orderly used to the first indicator of pumping, liquid to be detected and the second indicator.The present embodiment
In, liquid pump to be detected enters speed for 200 μ l/min, and the speed that is pumped into of the first indicator and the second indicator is respectively 40 μ l/
min.Here the liquid to be detected used can be Seawater Samples, be also possible to laboratory for the aqueous solution containing phosphate anion
The phosphate standard liquid of configuration, the first indicator and the second indicator are respectively ammonium molybdate solution and antimony tartrate potassium solution.This
In embodiment, the first indicator be by concentration be 0.14g/ml ammonium molybdate solution, the antimony tartrate potassium solution of 0.03g/ml,
The sulfuric acid solution of 0.92g/ml presses 18%, 2%, and 80% volume ratio mixes；Specific preparation method is as follows：Under stiring will
300ml sulfuric acid is slowly added in 600ml water and obtains sulfuric acid solution, weighs 28g ammonium molybdate, is dissolved in 200ml water and obtains molybdic acid
Ammonium salt solution, meanwhile, dissolution 6g potassium antimony tartrate obtains potassium antimony tartrate dissolution in 200ml water, finally, by 45ml molybdenum under stirring
Acid ammonium solution is added in 200ml sulfuric acid solution, and 5ml antimony tartrate potassium solution is added and is uniformly mixed so as to obtain mixed solution, is stored in
In Brown Glass Brown glass bottles and jars only, after solution becomes cloudy, prepare again.Second indicator is the ascorbic acid solution of 0.01g/ml, is specifically matched
The method of setting is：20g ascorbic acid is weighed in 200ml water, is stored in brown reagent bottle or polyethylene bottle, is kept in dark place at 4 DEG C,
It is prepared again after opaque.
Inlet portion 30 includes first entrance runner 31, second entrance runner 32, third entrance channel 33 and converges runner
34。
First entrance runner 31 and third entrance channel 33 are connected with miniflow pump 21 and 23 respectively, refer to for introducing first
Show agent and the second indicator.In the present embodiment, the width of first entrance runner 31 and third entrance channel 33 is 200 μm, deep
Degree is 125 μm.
Second entrance runner 32 is connected with miniflow pump 22, introduces liquid to be detected, when liquid to be detected is Seawater Samples, the
Need to install additional polymeric membrane filter 24 before two entrance channels 32, which, which refers to use, has certain pore size
Filter made of film (multi-purpose macromolecule polymer is material, such as cellulose acetate film and nylon membrane etc.), can remove in seawater
Microorganism, the substances such as silt and precipitating.In the present embodiment, the polymeric membrane filter for the use of aperture being 50 μm is used as to sea
Water is pre-processed, and 32 width of second entrance runner is 200 μm, and depth is 125 μm.In addition, second entrance runner 32 is also used to
It introduces ultrapure water and cleans channel.
The entrance for converging runner 34 is connected with first entrance runner 31, second entrance runner 32, third entrance channel 33.This
In embodiment, width is 200 μm, and depth is 125 μm, and length is in 2000-5000 μm.
As illustrated in fig. 1 and 2, mixing unit 40 includes multiple longitudinal miniflow channels 41, lateral miniflow channel 42 and semi-circular shape
Micro-structure 43.All longitudinal direction miniflow channels 41 are all arranged in parallel.All transverse direction miniflow channels 42 are also all arranged in parallel,
And each transverse direction miniflow channel 42 is located between two neighboring longitudinal miniflow channel 41.The setting of semi-circular shape micro-structure 43 is vertical
Into miniflow channel 41 and lateral miniflow channel 42, it is all provided in miniflow channel 41 longitudinally in each and each lateral miniflow channel 42
Set at least three semi-circular shape micro-structures 43.
In the present embodiment, in order to react liquid to be detected sufficiently with indicator and save the reaction time, by repetition test,
Six longitudinal miniflow channels 41 and five lateral miniflow channels 42 are set in mixing module.
Six longitudinal miniflow channels 41 are successively set as first to the 6th longitudinal miniflow channel 41 along direction F is flowed to.The
The end that becomes a mandarin of one longitudinal miniflow channel 41 is connected with the outlet for converging runner 34, and length is D1.Second to the 6th is longitudinal micro-
The equal length for flowing channel 41, is D2, D1：D2=1：1.5~3.In the present embodiment, the length of first longitudinal direction miniflow channel 41
D1=3256 μm, D2=6512 μm of length of second to the 6th longitudinal miniflow channel 41.As shown in Fig. 3 (a), in the present embodiment,
Longitudinal miniflow channel 41 is primary every 1000 μm of bendings, and curved radian is 180 °, 100 μm of curved part internal diameter, 300 μ of outer diameter
M, arc length are about 628 μm.
The equal length of five lateral miniflow channels 42, is B1, B1：D1=1：1.5~3.It is laterally micro- in the present embodiment
B1=1628 μm of length for flowing channel 42.
All longitudinal direction miniflow channels 41 are equal with the width of lateral miniflow channel 42, are W, W：D1=1：15~20.This
In embodiment, W=200 μm of width of all miniflow channels.
The outer diameter of semi-circular shape micro-structure 43 is E, E：W=3~8：12.In the present embodiment, semi-circular shape micro-structure 43
Internal diameter is 30 μm, E=60 μm of outer diameter；3 semi-circular shape micro-structures 43 are provided in first longitudinal direction miniflow channel 41；Second
30 semi-circular shape micro-structures 43 are each provided with into the 6th longitudinal miniflow channel 41；And it is set in each transverse direction miniflow channel 42
There are 6 semi-circular shape micro-structures 43.
In order to further promote liquid and indicator to be detected to be sufficiently mixed, and accelerate the anti-of liquid and indicator to be detected
It answers, semicircular ring is angled with channel in miniflow channel, and these micro-structures are not point-blank.So that be detected
Liquid can be sufficiently mixed in a mixer with indicator, and chromogenic reaction occurs.Specifically, in the present embodiment, micro- longitudinally in each
It flows in channel 41 and each lateral miniflow channel 42, with 280 μm or 150 μm of distance of center circle between adjacent semi-circular shape micro-structure 43
Unequally distributed blades, and the opening line of semi-circular shape micro-structure 43 and miniflow channel are axial at 60 ° or 120 ° of angle, and this
The center of circle of a little semi-circular shape micro-structures 43 is not point-blank.
As shown in figure 3, in order to there is more intuitive three-dimensional hybrid effect, by liquid to be detected rhodamine B reagent dyeing, and
By indicator rhodamine 6G reagent dyeing.It is pumped liquid to be detected and indicator by miniflow respectively with 200 μ l/min, 40 μ l/
The flow velocity of min is pumped into mixing module.By the way that respectively figure can be seen that liquid and indicator to be detected have obtained sufficiently in mixing unit in Fig. 3
Mixing, is greatly saved the reaction time.
50 entrance of capillary cuvette is connected with the stream end that goes out for longitudinal miniflow channel 41 that most downstream is arranged in.Capillary colorimetric
The depth of pipe 50 is 125 μm, and width is 300 μm.It is anti-that liquid and indicator to be detected are sufficiently mixed generation in liquid mixing unit 40
It should be introduced into capillary cuvette 50 afterwards.
In the present embodiment, the template of mixing unit 40 and capillary cuvette 50 is using organic material dimethyl silicone polymer
(Polydimethylsiloxane, abbreviation PDMS) material is made up of the ultraviolet photolithographic technology of standard：First according to design software
Figure is developed in silicon wafer, i.e., on PDMS mold then by ultraviolet photolithographic technology by the graphic making mask finished.Exist again
The not solidified PDMS of PDMS mold upper dries i.e. solidifiable in 1 hour in 75 degrees Celsius of at a temperature of heat, obtains semi-finished product；Through
It crosses cutting and finished product has just been obtained by plasma torch processing and glass slide bonding.
Optical fiber portion 60 includes two optical fiber 61 and 62, and the front port of two optical fiber 61 and 62 is mutually arranged oppositely in capillary colorimetric
The left and right sides of pipe 50, and optical film is coated on front port, so that forming optical resonator between two front ports.This reality
It applies in example, the outer diameter of two optical fiber 61 and 62 is 125 μm；The optical film used is golden film, the front port difference of two optical fiber
It is fixed in the left and right side walls of capillary cuvette 50, and the end face of front port is flushed with the inner surface of side wall, two front ports
End face be parallel to each other, form Fabry-Perot cavity, chamber is long be capillary cuvette width；Specifically, before optical fiber 61
Port is the golden film that 40nm thickness is plated in vacuum evaporation plating machine, and the front port of optical fiber 62 is that 60nm thickness is plated in vacuum evaporation plating machine
Golden film, and then form the mirror of two high refractive indexes, light roundtrip in the microcavity between two mirrors, light path obtains
Increase.
In the present embodiment, we are using optical fiber align device come to quasi-fiber 61 and 62.Optical fiber align device is by with reeded
Iron plate and magnetic pressure block composition.Firstly, placing the fiber in groove.Then, careful mobile base makes two optical fiber under the microscope
61 and 62 alignments.After alignment, a small amount of uv-curable glue is added, after ultraviolet light 3-5min, optical fiber can be fixed.?
The reserved channel of promising optical fiber, purple light solidification glue are incorporated into reserved channel in PDMS, and purple light solidification glue can play solid
Fixed and sealing effect, prevents liquid in capillary cuvette 50 from flowing out.
Laser source 70 is connected with the rear end of optical fiber 61, can issue the laser close to absorption peak wavelength (882nm).
Spectrometer 80 is connected with the rear end of optical fiber 62, and recording laser passes through the luminous intensity exported after capillary cuvette 50,
And it is compared to obtain absorbance value with laser normal intensity.
Waste collection portion 90 is connected with the outlet of capillary cuvette 50, collects the waste liquid of discharge.
It is the specific structure of optofluidic detector 10 provided by the present embodiment above, is based on above structure, the present embodiment
Phosphorus content in seawater is further measured using P-Mo blue spectrophotometry.In acid medium, phosphate and ammonium molybdate reaction
It is yellow to generate phosphorus molybdenum, after ascorbic acid is added, is reduced into P-Mo blue.Product property in acidic environment is stablized, in wavelength
Nearby there is stronger absorption peak for the light of 882nm, spectrophotometry easy to use is analyzed, molar absorption coefficient 3.6
×103mol-1cm-1.According to lambert-Beer law, the ratio that light is absorbed by transparent medium is unrelated with the intensity of incident light, in light
The light of every blanket layer Absorption of Medium same ratio value in journey, therefore (concentration is less than 0.01mol/L) absorbance can in weak solution
To be used to quantitatively calculate the phosphate concn in solution.Such detection mode, the not only good, high sensitivity of selectivity, accurate, steady
The advantages that fixed reliable, while micron order detection fine structure is combined again, thus the size and energy consumption of equipment can be substantially reduced, make
Quick nutritive salt detection is carried out with micro reagent consumption (microlitre, nanoliter).
Specifically, in the present embodiment for measuring the phosphorus content of phosphate radical titer, to optofluidic detector 10
Operating method is illustrated：
1. first ultrapure water is pumped into second entrance runner 32 using miniflow pump 22, flow velocity is 200 μ l/min, is continued
1min cleans channel, while can also be used as with reference to background, starts laser source 70 and spectrometer 80, and spectrometer 80 is remembered
The light intensity signal received at this time under record.
2. first indicator and the second indicator are first pumped into first entrance using miniflow pump 21 and 23 after cleaning
Runner 31 and third entrance channel 33, and then mixing unit 40 is flowed to, flow velocity is 40 μ l/min, then will filtering using miniflow pump 22
Liquid to be detected (in particular for Seawater Samples) afterwards is pumped into mixing unit 40 from second entrance runner 32, and flow velocity is also 200 μ l/
Min continues 2min, so that liquid to be detected is sufficiently mixed with indicator and reacts.
3. recording light intensity signal again, and it is compared to obtain the value of absorbance with the light intensity signal when first step.It utilizes
Langbobier law quantitatively calculates phosphatic concentration.It can also be using first drafting phosphate radical titer and absorbance curve table
Method, the phosphate concentration of solution to be measured is obtained by enquiry form and curve.
It is compound concentration is respectively 10 μm of ol/L, 40 μm of ol/L in the present embodiment, 60 μm of ol/L and 100 μm of ol/L's
Phosphate standard uses solution, then executes the test process of above-mentioned steps 1 to 3 respectively, to record various concentration respectively
Phosphate standard liquid passes through the light intensity signal detected after optofluidic detector 10, and is depicted as spectrogram as shown in Figure 4；Fig. 4
Show the light intensity signal that the phosphate standard liquid of various concentration is exported after colour developing by Fabry-Perot cavity, it can from figure
To find out the increase with phosphate concn, light intensity signal can weaken.Largest light intensity (0 μm of ol/L) is used as reference, according to youth
Primary-Beer law, spectrometer can calculate the phosphatic absorbance of each concentration, as shown in figure 5, absorbance and liquid to be detected are dense
There is good linear relationship between degree, and error range is no more than 10%, is consistent with primary-Beer law of youth, it was demonstrated that this programme
Effectively.Relative to traditional detection device, 10 detection range of optofluidic detector provided by the present embodiment has very big mention
It is high.Meanwhile passing through many experiments, it was demonstrated that the detectable limit of optofluidic detector 10 can achieve 0.1 μm of ol/L in this programme.
Above is only the illustration done to technical solution of the present invention.Phosphorus contains in measurement seawater according to the present invention
The optofluidic detector of amount is not merely defined in the structure described in above, but with claim limited range
Subject to.Any modify or supplement or equivalence replacement that those skilled in the art of the invention are done on the basis of this, all at this
In the claim of invention range claimed.
Claims (10)
1. the optofluidic detector of phosphorus content in a kind of measurement seawater, which is characterized in that including：
Three miniflow pumps, pump the first indicator, liquid to be detected and the second indicator respectively；
Inlet portion, comprising pumping the first entrance runner, second entrance runner, the third entrance channel that are connected with three miniflows respectively；
Mixing unit includes：Multiple longitudinal miniflow channels arranged in parallel, the adjacent longitudinal miniflow channel of multiple connections
Lateral miniflow channel, and the micro- knot of multiple semi-circular shape being arranged in longitudinal miniflow channel and the lateral miniflow channel
Structure, be arranged in become a mandarin end and the first entrance runner of longitudinal miniflow channel of most upstream, the second entrance runner,
It is connected with the outlet of the third entrance channel；
Capillary cuvette, entrance are connected with the stream end that goes out for longitudinal miniflow channel that most downstream is arranged in；
Optical fiber portion, includes two optical fiber, and the front port of two optical fiber is mutually arranged oppositely in the left and right of the capillary cuvette
Two sides, being coated with optical film on two front ports makes to form optical resonator between two ports；And
Laser source is connected with the rear end of the optical fiber, for emitting laser,
Wherein, the rear end of another optical fiber is connected with spectrometer, and the spectrometer recording laser is made to pass through the capillary ratio
The luminous intensity exported after colour tube, and be compared to obtain absorbance value with laser normal intensity.
2. the optofluidic detector of phosphorus content in measurement seawater according to claim 1, it is characterised in that：
Wherein, the second entrance runner is between the first entrance runner and the third entrance channel,
The miniflow pump for pumping liquid to be detected is connected with the second entrance runner.
3. the optofluidic detector of phosphorus content in measurement seawater according to claim 1, it is characterised in that：
Wherein, longitudinal miniflow channel altogether there are six, it is longitudinal micro- along flowing to direction for them and being successively set as first to the 6th
Channel is flowed, the length of the first longitudinal direction miniflow channel is D1, and the equal length of second to the 6th longitudinal miniflow channel is D2,
D1：D2=1：1.5~3,
There are five the transverse direction miniflow channel is total, length is B1, B1：D1=1：1.5~3,
The width of all longitudinal miniflow channels and the lateral miniflow channel is equal, is W, W：D1=1：15~20.
4. the optofluidic detector of phosphorus content in measurement seawater according to claim 3, it is characterised in that：
Wherein, D1=3256 μm of length of the first longitudinal direction miniflow channel, the length D2=of remaining longitudinal miniflow channel
6512 μm,
B1=1628 μm of length of the transverse direction miniflow channel,
W=200 μm of width of all miniflow channels.
5. the optofluidic detector of phosphorus content in measurement seawater according to claim 3, it is characterised in that：
Wherein, at least three semicircles are respectively provided in each longitudinal miniflow channel and each lateral miniflow channel
Annular micro-structure,
The outer diameter of the semi-circular shape micro-structure is E, E：W=3~8：12.
6. the optofluidic detector of phosphorus content in measurement seawater according to claim 5, it is characterised in that：
Wherein, the internal diameter of the semi-circular shape micro-structure be 30 μm, E=60 μm of outer diameter,
6 semi-circular shape micro-structures are equipped in each lateral miniflow channel,
3 semi-circular shape micro-structures are provided in the first longitudinal direction miniflow channel, in second to the 6th longitudinal miniflow
30 semi-circular shape micro-structures are each provided in channel,
In each longitudinal miniflow channel and each lateral miniflow channel, between the adjacent semi-circular shape micro-structure
Distance of center circle unequally distributed blades, and the center of circle of the adjacent semi-circular shape micro-structure is not point-blank.
7. the optofluidic detector of phosphorus content in measurement seawater according to claim 6, it is characterised in that：
Wherein, between the adjacent semi-circular shape micro-structure with 280 μm or 150 μm of distance of center circle unequally distributed blades, and it is described
The opening line and miniflow channel of semi-circular shape micro-structure are axial at 60 ° or 120 ° of angle.
8. the optofluidic detector of phosphorus content in measurement seawater according to claim 1, it is characterised in that：
Wherein, the optical film is golden film, and the front port of two optical fiber is separately fixed at the left and right of the capillary cuvette
On side wall, and the end face of the front port is flushed with the inner surface of the side wall.
9. the optofluidic detector of phosphorus content in measurement seawater according to claim 1, it is characterised in that：
Wherein, first indicator and second indicator are respectively ammonium molybdate solution and antimony tartrate potassium solution.
10. the optofluidic detector of phosphorus content in measurement seawater according to claim 1, which is characterized in that further include：
Waste collection portion is connected with the outlet of the capillary cuvette；With
The spectrometer.
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